Process for the preparation of poly(alkylene  terephthalate) employing in situ titanium-containing catalyst and compositions derived therefrom

ABSTRACT

Disclosed is a process for the manufacture of a polyalkylene terephthalate such as polybutylene terephthalate. In particular, the process comprises employing a titanium-containing catalyst formed by the reaction product of tctraalkyl titanate and a complexing agent comprising a phosphorous, nitrogen or boron atom. The process is used to prepare polyalkylene terephthalates characterized by improved hydrostability, as well as compositions derived therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/677,224, tiled Jul. 30, 2012, which isincorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

Disclosed is a process for the manufacture of a polyalkyleneterephthalate such as polybutylene terephthalate. In particular, theprocess comprises employing a titanium-containing catalyst formed by thereaction product of tetraalkyl titanate and a complexing agentcomprising a phosphorous, nitrogen or boron atom. The process is used toprepare polyalkylene terephthalates characterized by improvedhydrostability, as well as compositions derived therefrom.

BACKGROUND OF THE INVENTION

Polybutylene terephthalate (PBT) resin is a well-known polyalkyleneterephthalate that is semi-crystalline and has several desirableproperties alone or in blends. Compared to amorphous resins such asacrylonitrile butadiene styrene (ABS), polycarbonate, and polystyrene, asemi-crystalline resin like PBT can show higher solvent resistance,strength, and stiffness due to the presence of crystalline spherulitesin the resin. PBT resin is used in many applications in which itssolvent resistance, strength, rigidity, and lubricity are needed, mostcommonly in durable goods that are formed by injection molding. Throughits many blended products, PBT can be tailored to a wide variety ofapplications, including electronic and communications equipment,computers, televisions, kitchen and household appliances, industrialequipment, lighting systems, gardening and agricultural equipment,pumps, medical devices, food handling systems, handles, power and handtools, bobbins and spindles, and automotive parts in both under-the-hoodand exterior applications. Additionally, PBT is widely used to formelectrical connectors.

It is generally known that PBT can be made by reacting 1,4-butanediol(BDO) with terephthalic acid (TPA) or dimethyl terephthalate (DMT) inthe presence of a transesterification catalyst. U.S. Pat. Nos.7,129,301; 6,020,393; 4,328,059, and US Patent Pub. 2005/0113534 A1disclose various catalysts for the polymerization of polyesters.

Commonly used catalysts for the polymerization of PBT include tetraalkyltitanates. Among the various titanates are tetraisopropyl titanate,tetrabutyl titanate, and tetra(2-ethylhexyl) titanate. For example, JP60147430 discloses a method of producing polyester by esterifyingterephthalic acid, adipic acid and 1,4-butanediol in the presence of atitanium compound and a pentavalent phosphorus compound. U.S. Pat. No.6,303,738 discloses a process for producing copolyester containingadipic acid in the presence of TYZOR® IAM (available from DuPont), whichis prepared through the combination of tetraisopropyl titanate (TPT) anda mixture of butyl phosphate and dibutyl phosphate.

The catalyst used to prepare PBT is not typically quenched (deactivated)at the end of the polymerization process. Unfortunately, an activecatalyst in the resin composition can sometimes lead to undesirablereactions in subsequent processing of the polyalkylene terephthalate. Onexposure to high temperature and humidity, blends and compositionscontaining the polyalkylene terephthalate can exhibit hydrolyticdegradation. Another problem associated with the presence of the activecatalyst is transesterification, which can lead to loss of mechanicalproperties.

Catalyst quenchers such as phosphoric acid can be added to thermoplasticcompositions to prevent such transesterification, but they can alsopromote degradation of polymer chains and contribute to a decrease inpolymer molecular weight as well as greater hydrolytic instability. Theuse of phosphite stabilizers is less satisfactory because of thetendency for phosphites to be unstable to both hydrolysis and oxidation.Although the use of chain extenders can help to counterbalance theeffect of the quencher, it is desirable to eliminate the use of eitherquencher or chain extender additives as a necessity.

Insufficient hydrostahility of polyalkylene terephthalate can lead tochain cleavage, the extent of which depends on the exact conditions ofexposure to water or humidity. Temperature, time of exposure, and pH areall important. Both acids and bases can catalyze ester hydrolysis.Decomposition of polyalkylene terephthalate can be accelerated inaqueous acid or base, or if the polymer matrix of polyalkyleneterephthalate contains free acid or base additives. Since one of thereaction products of polyester hydrolysis is itself a carboxylic acid,the hydrolytic decomposition of PBT is autocatalytic, as depicted inScheme 1.

Thus, a need remains for new and improved catalysts or processes for theproduction of polyalkylene terephthalates that are effective inpolymerization, but which do not adversely impact the properties of theresulting polyalkylene terephthalate. There is also a need to eliminatethe necessity of using either quencher or chain extender additives inpreparing polyalkylene terephthalates. There is a further need forpolyalkylene terephthalates with improved properties includinghydrostability as well as polymer compositions derived therefrom.

SUMMARY OF THE INVENTION

These and other needs are met by the present invention which is directedto polyalkylene terephthalates that are prepared by employing apolyesterification catalyst that comprises a complex that is thereaction product of a tetra(C₁-C₈ alkyl) titanate and a compoundselected from phosphorus-containing compounds, nitrogen-containingcompounds, and boron-containing compounds. The catalyst can besynthesized in-situ, prior to ester interchange, for use during theester interchange and polymerization stages of the manufacturingprocess. Surprisingly, although the catalyst is not separated from thepolyalkylene terephthalates prior to isolation or further processing, itdoes not deleteriously affect the hydrostability or mechanicalperformance of the material.

The process of preparing a polyalkylene terephthalate comprises reactingan alkylene diol and a dicarboxy aromatic compound selected from thegroup consisting of aromatic dicarboxylic acids, aromatic dicarboxylic(C₁-C₃)alkyl esters, and combinations thereof, wherein the processcomprises forming a catalyst which consists of the reaction product of atetra(C₁-C₈ alkyl) titanate such as tetraisopropyl titanate and acomplexing agent. The complexing agent is selected from the groupconsisting of phosphorus-containing compounds, nitrogen-containingcompounds, boron-containing compounds, and combinations thereof;obtaining ester interchange by combining the catalyst with the alkylenediol and the aromatic dicarboxy compound; and polymerizing the productof ester interchange, in the continued presence of the catalyst. Thecatalyst is formed in-situ prior to the ester interchange stage,specifically formed in a solution comprising the alkylene diol, shortlybefore the ester interchange takes place; i.e., before the alkylene dioland diacid are combined, specifically within 48 hours, more specificallywithin 24 hours, for example, within a time space of 12 hours or less.

This process solves the problem in the prior art regarding undesirablepost-polymerization catalytic activity. In particular, as indicatedabove, the in-situ titanium-based catalyst system can improve hydrolyticstability, reduce or eliminate undesirable transesterification reactionsduring later processing, and thus improve mechanical performance.Furthermore, the catalyst system allows for the exclusion of catalystquenchers in thermoplastic compositions containing the polyalkyleneterephthalate resin. For example it is not necessary to add a catalystquencher during compounding or compounding of additives prior to orduring extrusion. As a result, because of the reduced amount or absenceof catalyst quencher during blending or compounding of the polyalkyleneterephthalate with other components, the resulting thermoplasticcomposition and articles made therefrom can show improved propertiessuch as increased hydrolytic stability.

In one aspect, the invention is directed to a polyalkylene terephthalatewith improved hydrostability, containing 50 to 300 ppm oftetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorouscontaining compound, both based on the total amount of titanium present,wherein the phosphorous containing compound is selected from the groupconsisting of phosphoric acid, poly(phosphoric acid), phosphorus acid,monobutyl phosphate, dibutyl phosphate, monoalkyl phosphates, dialkylphosphates, and combinations thereof. The tetra(C₁-C₈ alkyl) titanateand phosphorous containing compound are both present during the processfor making the polyalkylene terephthalate. Improved hydrostability isnot observed in the polyalkylene terephthalate when the phosphorouscontaining compound is not resident with the tetra(C₁-C₈ alkyl)titanate.

In this aspect and the other aspects and embodiments of the invention,the polyalkylene terephthalate is prepared from “virgin” startingmaterials and not from recycled polyester such as polyethyleneterephthalate. The virgin starting materials include alkylene diols anddicarboxy aromatic compounds selected from the group consisting ofaromatic dicarboxylic acids, aromatic dicarboxylic (C₁-C₃)alkyl esters,and combinations thereof.

Thus, the polyalkylene terephthalate that is used in the presentinvention is not a “modified polyalkylene terephthalate.” Modifiedpolyalkylene terephthalate, which includes “modified PBT,” is made fromrecycled or scrap polyethylene terephthalate (PET) wherein the polymeris modified by containing at least one residue derived from thepolyethylene terephthalate component used in the process. The residuecan be either incorporated into the structure of the polymer or presentin admixture with the resin composition. Thus, modified polyalkyleneterephthalates can identifiably differ slightly from PBT that is notmade from scrap PET (“virgin PBT”) by such modifications which, however,can be controlled so that the modified PBT has desirable propertiescomparable or similar to virgin PBT with little or no adverse effects.

Modified polyalkylene terephthalate can generally be made by reactingalkylene diol such as 1,4-butanediol with PET particulates, for exampletlakes, in the presence of a transesterification catalyst, for instance,as disclosed in U.S. Pat. No. 7,902,263. In general, processes forpreparing polyesters by depolymerizing aromatic polyesters in thepresence of polyols are known in the art. For example, U.S. Pat. No.5,451,611 describes a process for converting waste polyethyleneterephthalate (PET) to either poly(cthylene-co-butylene terephthalate)or polybutylene terephthalate by reaction with butanediol. Example 11 ofU.S. Pat. No. 5,451,611 patent shows a PBT polymer being formed with acomplete replacement of ethylene glycol by butanediol. U.S. Pat. No.5,266,601 and published U.S. Pat Application 20090275698 (A1) describe aprocess for making PBT from PET by reacting PET with butanediol.

In another aspect, the invention is directed to a hydrostablethermoplastic composition, comprising:

from 10 to 90 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate containing 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compound,both based on the total amount of titanium present, wherein thephosphorous containing compound is selected from the group consisting ofphosphoric acid, poly(phosphoric acid), phosphorus acid, monobutylphosphate, dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates,and combinations thereof; andfrom 10 to 90 percent by weight of a polycarbonate;wherein the polyalkylene terephthalate is not produced from recycledPET;wherein all weight percents are based on the total weight of thecomposition; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another aspect, the invention is directed to a hydrostablethermoplastic composition, comprising:

from 20 to 80 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate containing 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compound,both based on the total amount of titanium present, wherein thephosphorous containing compound is selected from the group consisting ofphosphoric acid, poly(phosphoric acid), phosphorus acid, monobutylphosphate, dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates,and combinations thereof; and

from 20 to 80 percent by weight of a polycarbonatefrom 0 to 30 percent by weight of an impact modifier or other polymer;andfrom 0 to 5 percent by weight of an additive selected from fillers thegroup consisting of reinforcing agents, anti-oxidants, heat stabilizers,light stabilizers, ultraviolet light (UV) absorbers, plasticizers,lubricants, mold release agents, antistatic agents, colorants, blowingagents, melt strength additives, flame retardants, and anti-drip agents,and combinations thereof;

and

wherein the polyalkylene terephthalate is not produced from recycledPET;wherein all weight percents are based on the total weight of thecomposition; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

These and other features, aspects, and advantages will become betterunderstood with reference to the following description and appendedclaims.

BRIEF DESCRIPTION OF THE FIGS.

FIG. 1 shows impact strength retention as a function of hydro-aging timefor a PBT-PC composition in which the PBT was prepared by the processdescribed herein.

DETAILED DESCRIPTION OF THE INVENTION

As used herein the singular forms “a,” “an,” and “the” include pluralreferents. The term “combination” is inclusive of blends, mixtures,alloys, reaction products, and the like.

Unless defined otherwise, technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill.Compounds are described using standard nomenclature. The term “and acombination thereof” is inclusive of the named component and/or othercomponents not specifically named that have essentially the samefunction.

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, and the like, used in the specification and claims are to beunderstood as in all instances by the term “about.” Various numericalranges are disclosed in this patent application. Because these rangesare continuous, they include every value between the minimum and maximumvalues. The endpoints of all ranges reciting the same characteristic orcomponent are independently combinable and inclusive of the recitedendpoint. Unless expressly indicated otherwise, the various numericalranges specified in this application are approximations. The term “frommore than 0 to” an amount means that the named component is present insome amount more than 0, and up to and including the higher namedamount.

All ASTM tests and data are from the 2003 edition of the Annual Book ofASTM Standards unless otherwise indicated.

With respect to the terms “terephthalic acid group” and “isophthalicacid group” (“diacid groups”) or “ethylene glycol group,” “butanediolgroup,” and “diethylene glycol group” (“diol groups) being used toindicate, for example, the weight percent (percent by weight) of thegroup in a molecule, the term “isophthalic acid group(s)” means thegroup or residue of isophthalic acid having the formula(—O(CO)C₆H₄(CO)—), the term “terephthalic acid group” means the group orresidue of isophthalic acid having the formula (—O(CO)C₆H₄(CO)—), theterm “diethylene glycol group” means the group or residue of diethyleneglycol having the formula (—O(C₂H₄)O(C₂H₄)—), the term “butanediolgroup” means the group or residue of butanediol having the formula(—O(C₄H₈)—), and the term “ethylene glycol group” means the group orresidue of ethylene glycol having the formula (—O(C₂H4)—).

The term “recycle” as used herein refers to any component that has beenmanufactured and either used or intended for scrap. Thus, a recycledpolyester can be polyester that has been used, for example in drinkingbottle, or that is a byproduct of a manufacturing process, for examplethat does not meet a required specification and therefore wouldotherwise be discarded or scrapped. Recycle materials can thereforecontain virgin materials that have not been utilized.

The prefix “bio-” or “bio-derived” as used herein means that thecompound or composition is ultimately derived from a biomass orbiological source, e.g., “bio-1,3-propane diol” is derived from abiological (e.g., plant or microbial source) rather than a petroleumsource. Similarly, the prefix “petroleum-” or “petroleum-derived” meansthat the compound or composition is ultimately derived from a petroleumsource, e.g., a “petroleum-derived polyethylene terephthalate is derivedfrom reactants that are themselves derived from petroleum.

The term “biomass” means living or dead biological matter that can bedirectly or subsequently converted to useful chemical substances thatare ordinarily derived from non-renewable hydrocarbon sources. Biomasscan include cellulosic materials, grains, starches derived from grains,fatty acids, plant based oils, as well as derivatives from these biomassexamples. Examples of useful chemical substances include and are notlimited to diols and monomers used to make diols. Biomass based butanediol can be obtained from several sources. For instance, the followingprocess can be used to obtain biomass-based 1,4-butane diol. Agriculturebased biomass, such as corn, can be converted into succinic acid by afermentation process that also consumes carbon dioxide. Such succinicacid is commercially available from several sources such as fromDiversified Natural Products Inc. under the trade name “BioAmber™”. Thissuccinic acid can be easily converted into I ,4-butane diol by processesdescribed in several published documents such as in U.S. Pat. No.4,096,156, incorporated herein in its entirety. Another process thatdescribes converting succinic acid into 1,4-butane diol is described inLife Cycles Engineering Guidelines, by Smith et al., as described in EPApublication EPA/600/R-1/101 (2001).

The term “contain” as it refers to a polyalkylene terephthalatecontaining the catalyst described herein, means that the catalyst, whichis synthesized in-situ, is present during formation of theterephthalate, so that the catalyst is present in the isolatedpolyalkylene terephthalate product.

In this application, parts per million (ppm) as relating, for instance,to ppm of tetra(C₁-C₈ alkyl) titanate and ppm of a phosphorouscontaining compound in the polyalkylene terephthalate or compositionsderived therefrom, is based on the total amount of titanium contained inthe polyalkylene terephthalate.

In this application, the phrase “wherein essentially no quencher for thecatalyst complex is added to the compounded thermoplastic composition”means that no quencher is added to the thermoplastic composition.

In the aspects and embodiments of the invention described herein,polyalkylene terephthalate is prepared from “virgin” starting materialand not from recycled PET.

Unless otherwise specified, amounts are indicated in percents by weight.

Process

The invention described herein is based on the discovery that it ispossible to produce polyalkylene terephthalate with improvedhydrostability using a novel titanium-containing catalyst complexcomprising the reaction product of a tetra(C₁-C₈ alkyl) titanate with acomplexing agent selected from the group consisting ofphosphorus-containing compounds, nitrogen-containing compounds,boron-containing compounds, and combinations thereof

The process used to prepare polyalkylene terephthalate containingaromatic dicarboxylic acid groups incorporated into the polyesterinvolves the reaction of a dicarboxy aromatic compound, for example anaromatic dicarboxylic acid, with an alkylene diol under conditionssufficient to form the polyester. Examples of the aromatic dicarboxylicacid group include isophthalic acid groups, terephthalic acid groups,and a combination thereof The aromatic dicarboxylic group in thepolyester can also be derived from corresponding di(C₁ to C₃) alkylesters. In a preferred embodiment, the aromatic dicarboxylic acid groupis derived from terephthalic acid or di(C₁-C₃)alkyl ester thereof.

The titanium catalyst comprises the reaction product of a tetra(C ₁-C₈alkyl) titanate such as tetraisopropyl titanate and a complexing agentselected from:

(1) phosphorus-containing compounds, at a molar ratio of thephosphorus-containing compound:titanate from 0.05:1 to less than orequal to 1.2:1, specifically 0.2:1 to 1.2:1, more specifically 0.3:1 to1.2:1, most specifically 0.5:1 to 1.2:1,(2) nitrogen-containing compounds, at a molar ratio of thenitrogen-containing compound:titanate from 0.05:1 to less than or equalto 2:1, specifically 0.2:1 to 1.2:1, more specifically 0.3:1 to 1.2:1,most specifically 0.5:1 to 1.2:1,(3) boron-containing compounds, at a molar ratio of the boron-containingcompound:titanate from 0.05:1 to less than or equal to 2:1, specifically0.2:1 to 1.2:1, more specifically 0.3:1 to 1.2:1, most specifically0.5:1 to 1.2:1, and(4) combinations thereof.

Phosphorus-containing compounds can include, for example, phosphoricacid, poly(phosphoric acid), phosphorous acid, monobutyl phosphate,dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates, andcombinations thereof Specifically, the phosphorous-containing compoundcan be a compound in which the phosphorus atom is bound to four oxygenatoms, more specifically a compound that is not a metallic salt. Thus,the catalyst can be the reaction product of a tetraalkyl titanate and aphosphorous-containing compound in which less than 50 mol %,specifically less than 25 mol %, more specifically essentially zero mol%, of the phosphorous-containing compound is associated with a metallicion, specifically Li, Na, K, Ca, Mg, Ba, Zn, or mixtures thereof Morespecifically, the phosphorous-containing compound comprises only onephosphorous atom per molecule. Thus, the formation of chelating ligandscan be excluded in preparing the catalyst. In one embodiment,phosphonate and phosphonic acid compounds are excluded.

In particular, the present process can comprise forming a catalyst insitu by combining a tetra(C₁-C₈ alkyl) titanate such as tetraisopropyltitanate with a complexing agent such as phosphoric acid and an alkylenediol, prior to transesterification and polymerization. By “in situ” ismeant that the catalyst, a titainium complex, is not premade but isformed during the process in the presence of one or more components ofthe process. Thus, the catalyst is present during thetransesterification and polymerization reactions.

In preparing the catalyst, the tetra(C₁-C₈ alkyl) titanate, for reactionwith the complexing agent, can be provided in a total amount of 25 to1000 ppm, based on the total weight of the composition. The catalyst canbe present in the process, during depolymerization and polymerization,in the amount of 10 to 1000 ppm, specifically 25 to 500 ppm, morespecifically 35 to 250 ppm, most specifically 45 to 200 ppm, of titanium(Ti) based on the total weight of the composition (as well as based onthe resulting solid product).

Nitrogen-containing compounds for forming the catalyst complex caninclude alkyl amines, aromatic amines, alkyl aromatic amines, alkanolamines, ammonium compounds, and combinations thereof.

Boron-containing compounds can include boric acid, boron alkoxides,boric oxides, boron halides, metaborates, monoalkyl borates, dialkylborates, trialkyl borates, borazines, and combinations thereof.

In reference to the nitrogen-containing, phosphorous-containing, andboron-containing compounds, the term “alkyl” refers to branched orstraight chain monovalent saturated groups comprising carbon andhydrogen, specifically having 1 to 12, more specifically 1 to 6, mostspecifically 1-3 carbon atoms. Specifically, alkanol can have ananalogous number of carbon atoms. Aromatic compounds have at least one,specifically one, two or three C₆-C₁₂ aryl groups (for example phenyl,naphthyl, or the like) containing only carbon in the aromatic ring,optionally substituted. Exemplary substituents can include halogen,cyano, nitro, hydroxyl, alkyl, alkoxy, arylalkoxy, and combinationsthereof.

In general, preparation of a polyalkylene terephthalate, specificallyPBT, by melt-process polycondensation is well known to those skilled inthe art. Conventional polycondensation procedures are described, forexample, in U.S. Pat. No. 2,012,267. Such reactions are typicallyoperated at temperatures from 150° C. to 300° C. in the presence of acatalyst employed in amounts between 10 to 1000 parts per million (ppm),based on total weight of the reactants. A branched polyalkyleneterephthalate can be prepared in which a branching agent, for example, aglycol having three or more hydroxyl groups or a trifunctional ormultifunctional carboxylic acid has been incorporated.

For example, conventional processes are known by which apoly(1,4-butylene terephthalate) or “PBT” resin can be obtained bypolymerizing a glycol component at least 90 mol %, specifically at least95 mol %, of which consists of tetramethylene glycol and an acid orester component at least 90 mol ° A), specifically at least 95 mol %, ofwhich consists of terephthalic acid. The present process can be used incooperation with, or adapted to, methods (or elements of methods)available in the prior art, as will be appreciated by one of ordinaryskill in the art.

As stated above, the present process of preparing a polyalkyleneterephthalate can be by melt polycondensation comprising reacting analkylene diol and a dicarboxy compound selected from the groupconsisting of an aromatic dicarboxylic acid, an aromatic dicarboxylic(C₁-C₃)alkyl ester, and combinations thereof, wherein ester interchangeand polymerization occurs in the presence of a catalyst formed byreaction of a tetra(C₁-C₈ alkyl) such as titanate tetraisopropyltitanate and a compound selected from phosphorus-containing compounds,nitrogen-containing compounds, boron-containing compounds, andcombinations thereof, wherein the catalyst is synthesized in situ.

In particular, the present process can comprise forming the catalyst insitu by combining the tetra(C₁-C₈ alkyl) titanate, complexing agent, andalkylene diol (prior to introduction of the aromatic dicarboxy compound)to form a first mixture, wherein the first mixture is subjected to heatat an elevated first temperature.

The aromatic dicarboxy compound can then be subsequently introduced,optionally with additional alkylene diol, into the first mixture to forma second mixture, which can be subjected to heat to obtain esterinterchange at an elevated second temperature, specifically at atemperature that is higher than the first temperature. In oneembodiment, the ester interchange is carried out until the production ofmethanol volatiles substantially ceases.

Polymerization can be initiated and carried out under vacuum, aftersubstantial completion of the ester interchange, by further increasingthe temperature to a third temperature higher than the secondtemperature. In particular, the second mixture can be subjected tovacuum, optionally with distillation, at a pressure of less than 2 Torrand a temperature of 220° C. to 270° C., to form molten polyalkyleneterephthalate.

By way of illustration, a titanium-containing catalyst comprising thereaction product of tetra(C₁-C₈ alkyl) titanate such as tetraisopropyltitanate and a phosphorous-containing compound, for example, phosphoricacid, can be formed in situ as shown in Scheme 2.

The in situ reaction between phosphoric acid and titanium isopropoxide(TPT) in diol solvent (for example, butanediol) can achieve a completeconversion in the reaction between the most acidic hydroxyl group of thephosphoric acid and TPT. Without wishing to be bound by theory, it isbelieved that once all strongly acidic hydroxyl groups are consumed, theester interchange and polymerization (polyesterification orpolycondensation) can be conducted without inhibition. After thecatalyst preparation, all the monomer components can be introduced intothe reactor, and the reaction temperature can be increased, for exampleto 220° C., to complete the ester interchange, followed bypolycondensation, for example, at 250° C.

The alkylene diol groups incorporated into the polyalkyleneterephthalate according to the present process can be derived from anyalkylene diol, including cyclic and non-cyclic alkylene diols, that canreact with the aromatic dicarboxy compound to form the polyalkyleneterephthalate. Examples of suitable alkylene diols can include ethyleneglycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol,2,3-butanediol, 1,4-butanediol, tetramethyl cyclobutanediol, cyclohexanedimethanol (including 1,2-, 1,3-, and 1,4-cyclohexane dimethanol),hexylene glycols, and combinations thereof. In one embodiment, thealkylene diol is selected from 1,4-butanediol, 1,3-propanediol, ethyleneglycol, and combinations thereof. Any of the foregoing alkylene diolscan be bio-derived from a biological source, for example, biomass.

The aromatic dicarboxy compound used in the present process can includedimethyl terephthalate derived from recycled PET. Processes forrecovering dimethyl terephthalate, also referred to as DMT or thedimethyl ester of terephthalic acid, are known in the art, for exampleas set forth in U.S. Pat. No. 6,472,557 and other patents disclosedtherein, which disclosure is incorporated herein by reference.Typically, the polyethylene terephthalate is reacted at elevatedtemperature and suitable conditions with an alcohol, such as methanol,to break the ester linkages of the polyester and yield the correspondingdiesters of the terephthalic acid, such as dimethyl terephthalate (DMT).

The present process excludes or limits the presence of aliphaticdicarboxylic acid monomers to form the polyalkylene terephthalate, whichmonomers comprise less than 5 wt. % of the polyalkylene terephthalate,specifically less than 2 wt. %, more specifically essentially zero wt.%. Thus, aliphatic dicarboxylic compounds having the general formula(CH₂)_(m)(COOH)₂, where m is an integer from 2 to 12, are excluded fromuse in preparing the polyalkylene terephthalate. Specifically, aliphaticdicarboxylic acids such as decanedioic acid, adipic acid, and sebacicacid are excluded or limited to insignificant amounts in the presentprocess.

Examples of polyalkylene terephthalate that can be prepared by thepresent process include, for example, polyethylene terephthalate(“PET”), poly(1,4-butylene terephthalate) (“PBT”), polypropyleneterephthalate (“PPT”), polycyclohexane terephthalate, copolyesters ofterephthalate esters with comonomers containing cyclohexyl dimethanoland ethylene glycol, copolyesters of terephthalate acid with comonomerscontaining cyclohexyl dimethanol and ethylene glycol, polytrimethyleneterephthalate, polydianol terephthalates, and combinations thereof

The process can also be employed to prepare a polyalkylene terephthalatethat is a copolyester derived from terephthalic acid (specificallyterephthalic acid and/or isophthalic acid) and a mixture comprising alinear C₂₋₆ aliphatic diol (specifically ethylene glycol and butyleneglycol); and a C₆₋₁₂ cycloaliphatic diol (specifically 1,4-cyclohexanediol, dimethanol decalin, dimethanol bicyclooctane, 1,4-cyclohexanedimethanol and its cis- and trans-isomers, 1,10-decane diol, and thelike). The ester units comprising the two or more types of diols can bepresent in the polymer chain as individual units or as blocks of thesame type of units. Specific esters of this type includepoly(1,4-cyclohexylene dimethylene co-ethylene terephthalate) (PCTG)wherein greater than 50 mol % of the ester groups are derived from1,4-cyclohexanedimethanol; and poly(ethylene-co-1,4-cyclohexylenedimethylene terephthalate) wherein greater than 50 mol% of the ester groups are derived from ethylene (PTCG). Thus, the term“alkylene diol” as used herein is meant to include both aliphatic andcycloaliphatic alcohols.

The process of preparing a polyalkylene terephthalate can compriserelatively lesser amounts of isophthalate groups and specifically lessthan 10 wt. %, more specifically less than 5 wt. %, most specificallyless than 2 wt. % of acid groups other than terephthalate groups,isophthalate groups, and alkylene diol groups (cyclic alkylene diolgroups and non-cyclic alkylene diol groups).

In one embodiment, the present process is used to prepare a polyalkyleneterephthalate having a number average molecular weight of at least15,000 g/mol, specifically 20,000 to 200,000 g/mol) and a polydispersityindex from 2 to less than 6, specifically 2 to 5. In such an embodiment,the polyalkylene terephthalate, specifically the PBT, has a meltingtemperature (T_(m)) ranging from 150° C. to 223° C., specifically 200°C. to 218° C., more specifically 204° C. to 210° C. The molecular weightcan be obtained using polystyrene standards, as measured by gelpermeation chromatography in chloroform/hexatluoroisopropanol (5:95,volume/volume ratio) at 25° C.

The polyalkylene terephthalate can have an intrinsic viscosity (asmeasured in phenol/tetrachloroethane (60:40, volume/volume ratio) at 25°C.) of 0.4 to 2.0 deciliters per gram. In one embodiment, the PBT resinhas an intrinsic viscosity of 0.6 to 1.4 dl/g.

The polyalkylene terephthalate prepared by the present process comprisesthe components of the titanium-containing catalyst. Thus, thepolyalkylene terephthalate prepared by the present process comprises 50to 300 ppm of tetra(C₁-C₈ alkyl) titanate and 100 to 600 ppm of aphosphorous containing compound, both based on the total amount oftitanium present, wherein the phosphorous containing compound isselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof. Morespecifically, the polyalkylene terephthalate prepared by the presentprocess is PBT, which comprises 50 to 300 ppm of tetraisopropyl titanateand 100 to 600 ppm of phosphoric acid.

In one embodiment, the present process is used to prepare a polyalkyleneterephthalate containing 50 to 300 ppm of tetra(C₁-C₈ alkyl) titanateand 100 to 600 ppm of a phosphorous containing compound, both based onthe total amount of titanium present, wherein the phosphorous containingcompound is selected from the group consisting of phosphoric acid,poly(phosphoric acid), phosphorus acid, monobutyl phosphate, dibutylphosphate, monoalkyl phosphates, dialkyl phosphates, and combinationsthereof. The polyalkylene terephthalate typically has a number averagemolecular weight of at least 15,000 g/mol, specifically 20,000 to200,000 g/mol) and a polydispersity index from 2 to less than 6,specifically 2 to 5. In such an embodiment, the polyalkyleneterephthalate, specifically the PBT, has a melting temperature (T_(m))ranging from 150° C. to 223° C., specifically 200° C. to 218° C., morespecifically 204° C. to 210° C. The molecular weight can be obtainedusing polystyrene standards, as measured by gel permeationchromatography in chloroform/hexafluoroisopropanol (5:95, volume/volumeratio) at 25° C.

In one embodiment, the polyalkylene terephthalate is polybutyleneterephthalate which contains 50 to 300 ppm of tetra(C₁-C₈alkyl) titanatewhich is tetraisopropyl titanate and 100 to 600 ppm of a phosphorouscontaining compound which is phosphoric acid. The PBT typically has anintrinsic viscosity (as measured in phenol/tetrachloroethane (60:40,volume/volume ratio) at 25° C.) of 0.4 to 2.0 deciliters per gram. Inone embodiment, the PBT resin has an intrinsic viscosity of 0.6 to 1.4dl/g.

In another aspect, the invention is directed to a polyalkyleneterephthalate prepared by a process comprising reacting a alkylene dioland a dicarboxy aromatic compound selected from the group consisting ofaromatic dicarboxylic acids, aromatic dicarboxylic (C₁-C₃)alkyl esters,and combinations thereof, wherein the process comprises:

forming a catalyst that consists of the reaction product of tetra(C₁-C₈alkyl) titanate and a complexing agent selected from the groupconsisting of phosphorus-containing compounds, a nitrogen-containingcompounds, a boron-containing compound, and combinations thereof;obtaining ester interchange by combining the catalyst with the alkylenediol and the aromatic dicarboxy compound; andpolymerizing the product of ester interchange, in the continued presenceof the catalyst, yielding polyalkylene terephthalate.

Compositions

The polyalkylene terephthalate resin prepared by the process describedherein can be blended with other components to obtain a thermoplasticblends. For example, a thermoplastic composition can include otherpolymers, in addition to the polyalkylene terephthalate prepared by theprocess disclosed herein. In particular, a polyalkylene terephthalateprepared by the process disclosed herein can be blended a polycarbonate.

Thus, in another embodiment, the invention is directed to athermoplastic composition comprising:

from 10 to 90 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate 50 to 300 ppm of tetra(C₁-C₈ alkyl)titanate and 100 to 600 ppm of a phosphorous containing compound, bothbased on the total amount of titanium present, wherein the phosphorouscontaining compound is selected from the group consisting of phosphoricacid, poly(phosphoric acid), phosphorus acid, monobutyl phosphate,dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates, andcombinations thereof; and 10 to 90 percent by weight of a polycarbonate;and wherein no quencher for the catalyst complex is added to thecompounded thermoplastic composition.

As used herein, the term “polycarbonate” means a composition havingrepeating structural carbonate units of the Formula (1):

in which the R¹ groups are aromatic, aliphatic, or alicyclic organicradicals. In one embodiment, at least 60 percent of the total number ofR¹ groups are aromatic organic radicals and the balance thereof arealiphatic, alicyclic, or aromatic radicals. In another embodiment, eachR¹ is an aromatic organic radical, for example a radical of the Formula(2):

-A¹-Y¹-A²   Formula 2

wherein each of A¹ and A² is a monocyclic divalent aryl radical and Y¹is a bridging radical having one or two atoms that separate A¹ from A².In an exemplary embodiment, one atom separates A¹ from A². Illustrativenon-limiting examples of radicals of this type are —O—, —S—, —S(O)—,—S(O₂)—, —C(O)-, methylene, cyclohexyl-methylene,2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene,cyclododecylidene, and adamantylidene. The bridging radical Y ¹ may be ahydrocarbon group or a saturated hydrocarbon group such as methylene,cyclohexylidene, or isopropylidene. In one specific embodiment, thepolycarbonate is a linear homopolymer derived from bisphenol A, in whicheach of A¹ and A² is p-phenylene and Y¹ is isopropylidene.

Polycarbonates may be produced by the reaction of dihydroxy compoundshaving the formula HO—R¹—OH, wherein R¹ is as defined above. Dihydroxycompounds suitable in an interfacial reaction include the dihydroxycompounds of formula (A) as well as dihydroxy compounds of formula (3)

HO-A¹-Y¹-A²-OH   Formula 3

wherein Y¹, A¹ and A² arc as described above. Also included arebisphenol compounds of general formula (4):

wherein R^(a) and R^(b) each represent a halogen atom or a monovalenthydrocarbon group and may be the same or different; p and q are eachindependently integers of 0 to 4; and X_(a) represents one of the groupsof formula (5):

wherein R^(e) and R^(d) each independently represent a hydrogen atom ora monovalent linear or cyclic hydrocarbon group and Re is a divalenthydrocarbon group.

Some illustrative, non-limiting examples of suitable dihydroxy compoundsinclude the following: resorcinol, 4-bromoresorcinol, hydroquinone,4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantine,(alpha,alpha'-bis(4-hydroxyphenyl)toluene,bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobi-indanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, and the like, as well as combinations comprisingat least one of the foregoing dihydroxy compounds.

Specific examples of the types of bisphenol compounds that may berepresented by formula (3) include 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane(hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane, and1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising atleast one of the foregoing dihydroxy compounds may also be used. Thepolycarbonate copolymers may be made by methods known in the art, suchas by the method described in U.S. Application Publication 2003/0149223.

In some embodiments, blends of at least two different polycarbonates areused. In some of these embodiments, blends of at least twopolycarbonates having different molecular weights are used. Branchedpolycarbonate are also useful as well as blends of a linearpolycarbonate and a branched polycarbonate. The branched polycarbonatesmay be prepared by adding a branching agent during polymerization. Thesebranching agents include polyfunctional organic compounds containing atleast three functional groups selected from hydroxyl, carboxyl,carboxylic anhydride, haloformyl, and mixtures of the foregoingfunctional groups. Specific examples include trimellitic acid,trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenylethane, isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha, alpha-dimethylbenzyl)phenol), 4-chlorofbrmyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents may be added ata level of 0.05 weight percent to 2.0 weight percent based on 100percent by weight of the polycarbonate. All types of polycarbonate endgroups are contemplated as being useful in the polycarbonate, providedthat such end groups do not significantly affect desired properties ofthe thermoplastic compositions.

Polycarbonates as used herein further include blends of polycarbonateswith other copolymers comprising carbonate chain units. A specificsuitable copolymer is a “polyester carbonate”, also known as acopolyester-polycarbonate. Such “polyester carbonate” copolymers furthercontain, in addition to recurring carbonate chain units of the formula(1), repeating units of formula (6)

wherein B is a divalent radical derived from a dihydroxy compound, andmay be, for example, a C₂₋₁₀ alkylene radical, a C₆₋₂₀ alicyclicradical, a C₆₋₂₀ aromatic radical or a polyoxyalkylene radical in whichthe alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4carbon atoms; and T is a divalent radical derived from a dicarboxylicacid, and may be, for example, a C₂₋₁₀ alkylene radical, a C₆₋₂₀alicyclic radical, a C₆₋₂₀ alkyl aromatic radical, or a C₆₋₂₀ aromaticradical. As used herein, polyester carbonate means compositions havingat least 5 mole percent of carbonate linkages relative to the molar sumof the carbonate and ester linkages.

In one embodiment, B is a C₂₋₆ alkylene radical. In another embodiment,B is derived from an aromatic dihydroxy compound of formula (7):

wherein each R^(k) is independently a halogen atom, a C₁₋₁₀ hydrocarbongroup, or a C₁₋₁₀ halogen substituted hydrocarbon group, and n is 0 to4. The halogen is usually bromine. Examples of compounds that may berepresented by the formula (7) include resorcinol, substitutedresorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol,5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenylresorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol,2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone;substituted hydroquinones such as 2-methyl hydroquinone, 2-ethylhydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butylhydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone,2,3,5,6-tetratluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, orthe like; or combinations comprising at least one of the foregoingcompounds.

Examples of aromatic dicarboxylic acid compounds that may be used toprepare the polyester carbonate include isophthalic or terephthalicacid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, and mixtures comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexane dicarboxylic acid, or mixtures thereof. Aspecific dicarboxylic acid comprises a mixture of isophthalic acid andterephthalic acid wherein the weight ratio of terephthalic acid toisophthalic acid is 10:1 to 0.2:9.8. In another specific embodiment, Bis a C₂₋₆ alkylene radical and T is p-phenylene, m-phenylene,naphthalene, a divalent cycloaliphatic radical, or a mixture thereofThis class of polyester carbonate includes the poly(alkyleneterephthalates). Suitable aliphatic dicarboxylic acids include succinicacid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, undecanoic diacid,dodecanoic diacid, maleic acid and fumaric acid. Rather than utilizingthe dicarboxylic acid per se, it is possible, and sometimes evenpreferred, to employ the reactive derivatives of the acid, such as thecorresponding acid halides, in particular the acid dichlorides and theacid dibromides in the interfacial polymerization method or esters suchas optionally substituted phenyl esters in the melt polymerizationmethod. Thus, for example, instead of using isophthalic acid,terephthalic acid, or mixtures thereof, it is possible to employisophthaloyl dichloride, terephthaloyl dichloride, and mixtures thereof.

Suitable polycarbonates can be manufactured by processes such asinterfacial polymerization or melt polymerization. Although the reactionconditions for interfacial polymerization may vary, an exemplary processgenerally involves dissolving or dispersing a dihydric phenol reactantin aqueous caustic soda or potash, adding the resulting mixture to asuitable water-immiscible solvent medium, and contacting the reactantswith a carbonate precursor in the presence of a suitable catalyst suchas tricthylamine or a phase transfer catalyst, under controlled pHconditions, e.g., 8 to 10. The most commonly used water immisciblesolvents include methylene chloride, 1,2-dichloroethane, chlorobenzene,toluene, and the like. Suitable carbonate precursors include, forexample, a carbonyl halide such as carbonyl bromide or carbonylchloride, or a haloformate such as a bishaloformate of a dihydric phenol(e.g., the bischloroformates of bisphenol A, hydroquinone, or the like)or a glycol (e.g., the bishaloformate of ethylene glycol, neopentylglycol, polyethylene glycol, or the like). Combinations comprising atleast one of the foregoing types of carbonate precursors may also beused.

Among the phase transfer catalysts that can be used are catalysts of theformula (R³)₄Q⁺X, wherein each R³ is independently the same or differentand is a C₁₋₁₀ alkyl group; Q is a nitrogen or phosphorus atom; and X isa halogen atom or a C₁₋₈ alkoxy group or C₆₋₁₈ aryloxy group. Exemplaryphase transfer catalysts include, for example, [CH₃(CH2)₃]₄NX,[CH₃(CH₂)₃]₄X, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH2)₄]₄NX,CH₃[CH₃(CH₂)₃]₃NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈alkoxy group or a C₆₋₁₈ aryloxy group. An effective amount of a phasetransfer catalyst can be 0.1 to 10 weight percent based on the weight ofbisphenol in the phosgenation mixture. In another embodiment aneffective amount of phase transfer catalyst can be 0.5 to 2 weightpercent based on the weight of bisphenol in the phosgenation mixture.All types of polycarbonate end groups are contemplated as being usefulin the thermoplastic composition, provided that such end groups do notsignificantly adversely affect desired properties of the compositions.

A chain stopper (also referred to as a capping agent) can be includedduring polymerization to form the polycarbonate. The chain stopperlimits molecular weight growth rate, and so controls molecular weight inthe polycarbonate. Exemplary chain stoppers include certainmono-phenolic compounds, mono-carboxylic acid chlorides, and/ormono-chlorofonnates. Mono-phenolic chain stoppers are exemplified bymonocyclic phenols such as phenol and C₁₋₂₂ alkyl-substituted phenolssuch as p-cumyl-phenol, resorcinol monobenzoate, and p- andtertiary-butyl phenol; and monoethers of diphenols, such asp-methoxyphenol. Alkyl-substituted phenols with branched chain alkylsubstituents having 8 to 9 carbon atom can be specifically mentioned.Certain mono-phenolic UV absorbers can also he used as a capping agent,for example 4-substituted-2-hydroxybenzophenones and their derivatives,aryl salicylates, monoesters of diphenols such as resorcinolmonobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like.

Mono-carboxylic acid chlorides can also be used as chain stoppers. Theseinclude monocyclic, mono-carboxylic acid chlorides such as benzoylchloride, C₁₋₂₂ allyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and combinations thereof;polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydridechloride, and naphthoyl chloride; and combinations of monocyclic andpolycyclic mono-carboxylic acid chlorides. Chlorides of aliphaticmonocarboxylic acids with less than or equal to 22 carbon atoms areuseful. Functionalized chlorides of aliphatic monocarboxylic acids, suchas acryloyl chloride and methacryoyl chloride, are also useful. Alsouseful are mono-chloroformates including monocyclic,mono-chloroformates, such as phenyl chloroformate, alkyl-substitutedphenyl chloroformate, p-cumyl phenyl chloroformate, toluenechloroformate, and combinations thereof.

Alternatively, melt processes may be used to make the polycarbonate.Generally, in _(t)he melt polymerization process, polycarbonates may beprepared by co-reacting, in a molten state, the dihydroxy reactant(s)and a diaryl carbonate ester, such as diphenyl carbonate, in thepresence of a transesterification catalyst in a Banbury® mixer, twinscrew extruder, or the like to form a uniform dispersion. Volatilemonohydric phenol is removed from the molten reactants by distillationand the polymer is isolated as a molten residue.

Blends and/or mixtures of more than one polycarbonate may also be used.For example, a high flow and a low flow polycarbonate may be blendedtogether. In one embodiment, a blend and/or mixture of linearpolycarbonates having a weight average molecular weight relative topolycarbonate standards of less than 31,000 Daltons, specificallybetween 18,000 and 31,000 Daltons, is used.

In one embodiment, the polycarbonate is a2,2-bis(4-hydroxyphenyl)propane (bisphenol-A) polycarbonate,commercially available under the trade designation LEXAN.

In another embodiment, the polycarbonate can be a polycarbonate-siloxanecopolymer. The polydiorganosiloxane blocks comprise repeating structuralunits of the formula (sometimes referred to herein as “siloxane”):

wherein each occurrence of R is same or different, and is a C₁₋₁₃monovalent organic radical. For example, R may be a C₁₋₁₃ alkyl group,C₁₋₁₃ alkoxy group, C₂₋₁₃ alkenyl group, C₂₋₁₃ alkenyloxy group, C₃₋₆cycloalkyl group, C₃₋₆ cycloalkoxy group, C₆₋₁₀ aryl group, C₆₋₁₀aryloxy group, C₇₋₁₃ aralkyl group, C₇₋₁₃ aralkoxy group, C₇₋₁₃ alkarylgroup, or C₇₋₁₃ alkaryloxy group. Combinations of the foregoing R groupsmay be used in the same copolymer.

The value of D in

may vary widely depending on the type and relative amount of eachcomponent in the thermoplastic composition, the desired properties ofthe composition, and like considerations. Generally, D may have anaverage value of 2 to about 1000, specifically about 2 to about 500,more specifically about 5 to about 100. In one embodiment, D has anaverage value of about 10 to about 75, and in still another embodiment,D has an average value of about 40 to about 60. Where D is of a lowervalue, e.g., less than about 40, it may be desirable to use a relativelylarger amount of the polycarbonate-polysiloxane copolymer. Conversely,where D is of a higher value, e.g., greater than about 40, it may benecessary to use a relatively lower amount of thepolycarbonate-polysiloxane copolymer.

A combination of a first and a second (or more)polycarbonate-polysiloxane copolymers may be used, wherein the averagevalue of D of the first copolymer is less than the average value of D ofthe second copolymer.

In one embodiment, the polydiorganosiloxane blocks are provided byrepeating structural units of the formula:

wherein D is as defined above; each R may be the same or different, andis as defined above; and Ar may be the same or different, and is asubstituted or unsubstituted C₆₋₃₀ arylene radical, wherein the bondsare directly connected to an aromatic moiety. Suitable Ar groups in thisformula may be derived from a C₆₋₃₀ dihydroxyarylene compound, forexample a dihydroxyarylene compound of formula HO-A¹-Y¹-A²-OH,

or

above. Combinations comprising at least one of the foregoingdihydroxyarylene compounds may also be used. Specific examples ofsuitable dihydroxyarlyene compounds are 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane,2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenylsulphide), and 1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinationscomprising at least one of the foregoing dihydroxy compounds may also beused.

Such units may be derived from the corresponding dihydroxy compound ofthe following formula:

wherein Ar and D are as described above. Such compounds are furtherdescribed in U.S. Pat. No. 4,746,701 to Kress et al. Compounds of thisformula may be obtained by the reaction of a dihydroxyarylene compoundwith, for example, an alpha,omega-bisacetoxypolydiorangonosiloxane underphase transfer conditions.

In another embodiment the polydiorganosiloxane blocks comprise repeatingstructural units of the formula:

wherein R and D are as defined above. R² in this formula is a divalentC₂₋₈ aliphatic group. Each M in this formula may be the same ordifferent, and may be a halogen, cyano, nitro, C₁₋₈ alkylthio, C₁₋₈alkyl, C₁₋₈ alkoxy, alkenyl, C₂₋₈ alkenyloxy group, C₃₋₈ cycloalkyl,C₃₋₈ cycloalkoxy, C_(6.10) aryl, C₆₋₁₀ aryloxy, C₇₋₁₂ aralkyl, C₇₋₁₂aralkoxy, C₇₋₁₂ alkaryl, or C₇₋₁₂ alkaryloxy, wherein each n isindependently 0, 1, 2, 3, or 4.

In one embodiment, M is an alkyl group such as methyl, ethyl, or propyl,an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl groupsuch as phenyl or tolyl; R² is a dimethylene, trimethylene ortetramethylene group; and R is a C₁₋₈ alkyl, cyanoalkyl, or aryl such asphenyl, or tolyl. In another embodiment, R is methyl or a mixture ofmethyl and phenyl. In still another embodiment, M is methoxy, n is one,R² is a divalent C₁₋₃ aliphatic group, and R is methyl.

These units may be derived from the corresponding dihydroxypolydiorganosiloxane:

wherein R, D, M, R², and n are as described above.

Such dihydroxy polysiloxanes can be made by effecting a platinumcatalyzed addition between a siloxane hydride of the formula:

wherein R and D are as previously defined, and an aliphaticallyunsaturated monohydric phenol. Suitable aliphatically unsaturatedmonohydric phenols included, for example, eugenol, 2-alkylphenol,4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol,2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol,2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol.Mixtures comprising at least one of the foregoing may also be used.

A polycarbonate-polysiloxane copolymer may he manufactured by reactionof diphenolic polysiloxane with a carbonate source and a dihydroxyaromatic compound, optionally in the presence of a phase transfercatalyst as described above. Suitable conditions are similar to thoseuseful in forming polycarbonates. For example, the copolymers areprepared by phosgenation, at temperatures from below 0° C. to about 100°C., desirably about 25° C. to about 50° C. Since the reaction isexothermic, the rate of phosgene addition may be used to control thereaction temperature. The amount of phosgene required will generallydepend upon the amount of the dihydric reactants. Alternatively, thepolycarbonate-polysiloxane copolymers may be prepared by co-reacting ina molten state, the dihydroxy monomers and a diaryl carbonate ester,such as diphenyl carbonate, in the presence of a transesterificationcatalyst as described above. Siloxane groups may also he present at orattached to the ends of the copolymer as well.

In the production of a polycarbonate-polysiloxane copolymer, the amountof dihydroxy polydiorganosiloxane is selected so as to provide thedesired amount of polydiorganosiloxane units in the copolymer. Theamount of polydiorganosiloxane units may vary widely, i.e., may be about1 wt % to about 99 wt % of polydimethylsiloxane, or an equivalent molaramount of another polydiorganosiloxane, with the balance being carbonateunits. The particular amounts used will therefore be determineddepending on desired physical properties of the thermoplasticcomposition, the value of D (within the range of 2 to about 1000), andthe type and relative amount of each component in the thermoplasticcomposition, including the type and amount of polycarbonate, type andamount of impact modifier, type and amount of polycarbonate-polysiloxanecopolymer, and type and amount of any other additives. Suitable amountsof dihydroxy polydiorganosiloxane can be determined by one of ordinaryskill in the art without undue experimentation using the guidelinestaught herein. For example, the amount of dihydroxy polydiorganosiloxanemay be selected so as to produce a copolymer comprising about 1 wt % toabout 75 wt %, or about 1 wt % to about 50 wt % polydimethylsiloxane, oran equivalent molar amount of another polydiorganosiloxane. In oneembodiment, the copolymer comprises about 5 wt % to about 40 wt %,optionally about 5 wt % to about 25 wt % polydimethylsiloxane, or anequivalent molar amount of another polydiorganosiloxane, with thebalance being polycarbonate. In a particular embodiment, the copolymermay comprise about 20 wt % siloxane.

In specific embodiments, the polycarbonate is derived from a dihydroxycompound having the structure of the Formula:

wherein R₁ through R₈ are each independently selected from hydrogen,halogen, nitro, cyano, C₁₋₂₀ alkyl, C₄₋₂₀ cycloalkyl, and C₆₋₂₀ aryl;and A is selected from a bond, —O—, —S—, —SO₂, C₁₋₁₂ alkyl, C₆₋₂₀aromatic, and C₆₋₂₀ cycloaliphatic.

In specific embodiments, the dihydroxy compound of Formula (I) is2,2-bis(4-hydroxyphenyl) propane (i.e. bisphenol-A or BPA). Otherillustrative compounds of Formula (I) include:2,2-bis(4-hydroxy-3-methylphenyl)propane;2,2-bis(4-hydroxy-3-isopropylphenyl)propane;2,2-bis(3-t-butyl-4-hydroxyphenyl)propane;2,2-bis(3-phenyl-4-hydroxyphenyl)propane;1,1-bis(4-hydroxyphenyl)cyclohexane; 4,4′dihydroxy-1,1-biphenyl;4,4′-dihydroxy-3,3′-dimethyl-1,1-biphenyl;4,4′-dihydroxy-3,3′-dioctyl-1,1-biphenyl; 4,4′-dihydroxydiphenylether;4,4′-dihydroxydiphenylthioether; and1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene.

The polyorganosiloxane-polycarbonate can comprise 50 to 99 wt. % ofcarbonate units and 1 to 50 wt. % siloxane units. Within this range, thepolyorganosiloxane- polycarbonate copolymer can comprise 70 to 98 wt. %,more specifically 75 to 97 wt. % of carbonate units and 2 to 30 wt. %,more specifically 3 to 25 wt. % siloxane units.

Polyorganosiloxane-polycarbonates can have a weight average molecularweight of 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltonsas measured by gel permeation chromatography using a crosslinkedstyrene-divinyl benzene column, at a sample concentration of 1 milligramper milliliter, and as calibrated with polycarbonate standards.

The polyorganosiloxane-polycarbonate can have a melt volume flow rate,measured at 300° C./1.2 kg, of 1 to 50 cubic centimeters per 10 minutes(cc/10 min), specifically 2 to 30 cc/10 min. Mixtures ofpolyorganosiloxane-polycarbonates of different flow properties can beused to achieve the overall desired flow property.

In one embodiment, Polycarbonate B is Polycarbonate-Polydimethylsiloxanecopolymer containing approximately 18 to 20 percent siloxane. Thepolycarbonate-polysiloxane copolymer has a weight average molecularweight of 28,000 to 32,000.

Specifically, the polycarbonate-siloxane block copolymer can have thefollowing formula:

wherein x is 30-50, specifically about 40, y is 10-30, specificallyabout 20, and z is 45-60, specifically about 50 or 55.

In one embodiment, the thermoplastic composition comprises about 10 to90 percent of the polycarbonate. In another embodiment, thethermoplastic composition comprises about 20 to 80 percent of thepolycarbonate. In another embodiment, the thermoplastic compositioncomprises about 30 to 70 percent of the polycarbonate. In anotherembodiment, the thermoplastic composition comprises about 40-60 percentof the polycarbonate. Specifically, the polycarbonate is a bisphenolpolycarbonate or mixture of polycarbonates.

Thus, in a specific embodiment, the thermoplastic composition comprises:

from 20 to 80 percent by weight of a PBT prepared as described herein,wherein the polyalkylene terephthalate contains 50 to 300 ppm oftetra(C₁-C₈ alkyl) titanate and 100 to 600 ppm of a phosphorouscontaining compound, both based on the total amount of titanium present,wherein the phosphorous containing compound is selected from the groupconsisting of phosphoric acid, poly(phosphoric acid), phosphorus acid,monobutyl phosphate, dibutyl phosphate, monoalkyl phosphates, dialkylphosphates, and combinations thereof; andfrom 20 to 80 percent by weight of a bisphenol polycarbonate or mixtureof polycarbonates.

Thus, in a specific embodiment, the thermoplastic composition comprises:

from 30 to 70 percent by weight of a PBT prepared as described herein,wherein the polyalkylene terephthalate contains 50 to 300 ppm oftetra(C₁-C₈ alkyl) titanate and 100 to 600 ppm of a phosphorouscontaining compound, both based on the total amount of titanium present,wherein the phosphorous containing compound is selected from the groupconsisting of phosphoric acid, poly(phosphoric acid), phosphorus acid,monobutyl phosphate, dibutyl phosphate, monoalkyl phosphates, dialkylphosphates, and combinations thereof; andfrom 30 to 70 percent by weight of a bisphenol polycarbonate or mixtureof polycarbonates.

In another specific embodiment, the thermoplastic composition comprises:

from 20 to 80 percent by weight of a PBT prepared as described herein,wherein the polyalkylene terephthalate contains 50 to 300 ppm oftetra(C₁-C₈ alkyl) titanate and 100 to 600 ppm of a phosphorouscontaining compound, both based on the total amount of titanium present,wherein the phosphorous containing compound is selected from the groupconsisting of phosphoric acid, poly(phosphoric acid), phosphorus acid,monobutyl phosphate, dibutyl phosphate, monoalkyl phosphates, dialkylphosphates, and combinations thereof; andfrom 20 to 80 percent by weight of a bisphenol polycarbonate or mixtureof polycarbonates;from 0 to 30 percent by weight of an impact modifier or other polymer;and from 0 to 5 percent by weight of an additive selected from fillersthe group consisting of reinforcing agents, anti-oxidants, heatstabilizers, light stabilizers, ultraviolet light (UV) absorbers,plasticizers, lubricants, mold release agents, antistatic agents,colorants, blowing agents, melt strength additives, flame retardants,and anti-drip agents, and combinations thereof; andwherein the polyalkylene terephthalate is not produced from recycledPET;wherein all weight percents are based on the total weight of thecomposition; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another specific embodiment, the thermoplastic composition comprises:

from 20 to 50 percent by weight of a PBT prepared as described herein,wherein the polyalkylene terephthalate contains 50 to 300 ppm oftetra(C₁-C₈ alkyl) titanate and 100 to 600 ppm of a phosphorouscontaining compound, both based on the total amount of titanium present,wherein the phosphorous containing compound is selected from the groupconsisting of phosphoric acid, poly(phosphoric acid), phosphorus acid,monobutyl phosphate, dibutyl phosphate, monoalkyl phosphates, dialkylphosphates, and combinations thereof; andfrom 20 to 80 percent by weight of a bisphenol polycarbonate or mixtureof polycarbonates;from 0 to 30 percent by weight of an impact modifier or other polymer;andfrom 0 to 5 percent by weight of an additive selected from fillers thegroup consisting of reinforcing agents, anti-oxidants, heat stabilizers,light stabilizers, ultraviolet light (UV) absorbers, plasticizers,lubricants, mold release agents, antistatic agents, colorants, blowingagents, melt strength additives, flame retardants, and anti-drip agents,and combinations thereof; andwherein the polyalkylene terephthalate is not produced from recycledPET;wherein all weight percents are based on the total weight of thecomposition; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

As indicated by the previous embodiment, other additives can be added tothe polyalkylene terephthalate-polycarbonate thermoplastic blends forthe purpose of imparting properties desirable in the product being made.Additives are ordinarily incorporated into polymer compositions with theproviso that the additives are selected so as to not significantlyadversely affect the desired properties of the composition, for example,impact, flexural strength, color, and the like. Such additives can bemixed at a suitable time during the mixing of the components for formingthe composition. Possible additives include impact modifiers, fillers,reinforcing agents, anti-oxidants, heat stabilizers, light stabilizers,ultraviolet light (UV) absorbers, plasticizers, lubricants, mold releaseagents, antistatic agents, colorants, blowing agents, melt strengthadditives, flame retardants, and anti-drip agents. A good source forinformation relating to additives is the Plastics Additives Handbook,6^(th) ed. (Hans Zweifel, Ed., 2009).

Combinations of additives can be used, for example, an antioxidant, a UVabsorber, and a mold release agent. The total amount of additives (otherthan any impact modifier, tiller, or reinforcing agents) is generally0.01 to 15 percent by weight, based on the total weight of thecomposition.

Thus, in another embodiment, in addition to a polyalkylene terephthalateprepared as described herein and a polycarbonate, the thermoplasticcomposition further comprises an impact modifier. Many impact modifiersare known and are commercially available. Such impact modifiers aretypically high molecular weight elastomeric materials derived fromolefins, monovinyl aromatic monomers, acrylic and methacrylic acids andtheir ester derivatives, as well as conjugated dienes. The polymersformed from conjugated dienes can be fully or partially hydrogenated.The elastomeric materials can be in the form of homopolymers orcopolymers, including random, block, radial block, graft, and core-shellcopolymers. Combinations of such impact modifiers can be used.

An example of specific type of impact modifier is an elastomer-modifiedgraft copolymer comprising (i) an elastomeric (i.e., rubbery) polymersubstrate having a Tg less than about 10° C., more specifically lessthan about −10° C., or more specifically about −40° to −80° C., and (ii)a rigid polymeric superstrate grafted to the elastomeric polymersubstrate. Materials suitable for use as the elastomeric phase include,for example, conjugated diene rubbers, for example polybutadiene andpolyisoprene; copolymers of a conjugated diene with less than about 50wt. % of a copolymerizable monomer, for example a monovinylic compoundsuch as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate;olefin rubbers such as ethylene propylene copolymers (EPR) orethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetaterubbers; silicone rubbers; elastomeric C₁₋₈ alkyl(meth)acrylates;elastomeric copolymers of C₁₋₈ alkyl(meth)acrylates with butadieneand/or styrene; or combinations comprising at least one of the foregoingelastomers. Materials suitable for use as the rigid phase include, forexample, monovinyl aromatic monomers such as styrene and alpha-methylstyrene, and monovinylic monomers such as acrylonitrile, acrylic acid,methacrylic acid, and the C₁-C₆ esters of acrylic acid and methacrylicacid, specifically methyl methacrylate.

Specific exemplary elastomer-modified graft copolymers include thoseformed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber(SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS(acrylonitrile-butadiene-styrene),acrylonitrile-ethylene-propylene-diene-styrene (AES),styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene(MBS), and styrene-acrylonitrile (SAN).

Other impact modifiers include an epoxy-functional copolymer comprisingunits derived from a C₂-C₂₀ olefin and units derived from aglycidyl(meth)acrylate. Exemplary olefins include ethylene, propylene,butylene, and the like. The olefin units can be present in the copolymerin the form of blocks, e.g., as polyethylene, polypropylene,polybutylene, and the like blocks. It is also possible to use mixturesof olefins, i.e., blocks containing a mixture of ethylene and propyleneunits, or blocks of polyethylene together with blocks of polypropylene.

In addition to glycidyl(meth)acrylate units, the copolymers can furthercomprise additional units, for example C₁-C₄ alkyl(meth)acrylate units.In one embodiment, the impact modifier is terpolymeric, comprisingpolyethylene blocks, methyl acrylate blocks, and glycidyl methacrylateblocks. Specific impact modifiers are a co- or ter-polymer includingunits of ethylene, glycidyl methacrylate (GMA), and methyl acrylate,available under the trade name LOTADER® polymer, sold by Arkema. Theterpolymers comprise, based on the total weight of the copolymer, 0.3 to12 wt. % of glycidyl methacrylate units, more specifically 0.4 to 11 wt.% of glycidyl methacrylate units, even more specifically 0.5 to 10 wt. %of glycidyl methacrylate units. Suitable impact modifiers include theethylene-methyl acrylate-glycidyl methacrylate terpolymer comprising 8wt. % glycidyl methacrylate units available under the trade name LOTADERAX8900.

Specifically, such impact modifiers include methylmeth(acrylate)-butadiene-styrene, acrylonitrile-butadiene-styrene,styrene-ethylene/butylene-styrene, ethylene-glycidyl methacrylate-methylacrylate, ethylene-glycidyl(meth)acrylate-methyl acrylate impactmodifier, and combinations thereof.

In one embodiment, the thermoplastic composition comprises 0.01 to 20percent by weight of an impact modifier. More particularly, about 1 to20 percent by weight of the impact modifier is present in thethermoplastic composition of the invention. More particularly, about 5to 15 percent by weight of the impact modifier is present in thethermoplastic composition of the invention. In a particular embodiment,the impact modifier is a methylmethacrylate butadiene styrene (MBS) usedalone or with linear low density polyethylene (LLDPE).

In addition to the PBT prepared by the process disclosed herein, thepolycarbonate, and the impact modifier, the thermoplastic compositioncontains a stabilizer. The stabilizer can be a mixture of stabilizers,such as anti-oxidants, heat stabilizers, light stabilizers, orultraviolet light (UV) absorbers. Many impact modifiers are known andare commercially available. The total amount of stabilizer used istypically from 0.01 to 5 percent by weight, and more particularly from0.01 to 3 percent by weight. In a particular embodiment, pentaerythritolbetalaurylthiopropionate and one or more additional stabilizers ispresent in the thermoplastic composition. In a further embodiment, theadditional stabilizer is pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-)propionate). In aparticular embodiment, 0.01 to 1 percent by weight of pentaerythritolbetalaurylthiopropionate is present in the composition and 0.01 topercent by weight of the pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-) propionate). In a moreparticular embodiment, 0.01 to 0.1 percent by weight of pentaerythritolbetalaurylthiopropionate is present in the composition and 0.01 to 0.1percent by weight of the pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-)propionate).

In addition to the above-described additives, used accessorily in asmall amount, depending on the object, other polymers or resins,typically in an amount less than 50 weight percent, specifically lessthan 30 percent by weight, more specifically less that 20 percent byweight, of the total composition, can be added to the thermoplasticresin composition containing the polyethylene terephthalate. Forexample, such additional polymers can include polyamides, polyphenylenesulfide, polyphenylene oxide, polyacetal, acrylonitrile-styrene resin,acrylonitrile-butadiene-styrene resin, polysulfone, polyesteramides,polyether sulfone, polyether imide, polyether ketone, fluorine resin,and combinations thereof.

In addition to polyalkylene terephthalate and polycarbonate, otherpolyesters can optionally be present in the composition (in an amount ofless than 50 weight percent, specifically less than 30 percent byweight, more specifically less that 20 percent by weight, mostspecifically less than 10 percent by weight of the total composition,provided that such polyesters do not significantly and adversely affectthe desired properties of the composition.

For example, a thermoplastic composition can include, in addition to thepolyethylene terephthalate prepared by the present process otheraromatic polyesters, cycloaliphatic polyesters, and the like. Theadditional polyesters can be virgin polyesters or wholly or partiallybio-derived, including petroleum-derived aromatic polyesters andbio-derived aromatic polyesters.

The thermoplastic composition prepared as described herein ischaracterized by the intentional exclusion of a catalyst quencher suchas an acid interchange quencher from the composition. Thus, a processaccording to the present invention can be further characterized byexcluding (not adding) a catalyst quencher as a means for quenching thecatalyst in the thermoplastic composition containing the polyalkyleneterephthalate resin composition.

As indicated previously, quenchers are agents that inhibit activity ofany catalysts that can be present in the thermoplastic composition, inorder to prevent an accelerated interpolymerization and degradation ofthe polymer in the thermoplastic composition. Such quenchers areselected from the group consisting of acidic phosphate salts, acidphosphites, alkyl phosphites, aryl phosphites, mixed phosphites andcombinations thereof, specifically acidic phosphate salts; acidphosphites, alkyl phosphites, aryl phosphites or mixed phosphites havingat least one acidic hydrogen; a Group IB or Group IIB metal phosphatesalt; a phosphorus oxo acid, a metal acid pyrophosphate or a mixturethereof. The acidic phosphate salts can include sodium dihydrogenphosphate, mono zinc phosphate, potassium hydrogen phosphate, calciumdihydrogen phosphate and the like. Specific quenchers are phosphoricacid, phosphorous acid or their partial esters such as mono zincphosphate. More specifically, quenchers can include zinc phosphate,monozinc phosphate, phosphorous acid, phosphoric acid diluted in water,sodium acid pyrophosphate, tetrapropylorthosilicate,tetrakis-(2-methoxyethoxy)silane), sodium Iauryl sulphate, boric acid,citric acid, oxalic acid, a cyclic iminoether containing compound, andcombinations thereof

In one embodiment, the thermoplastic composition, comprises

from 30 to 70 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate containing 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compound,both based on the total amount of titanium present, wherein thephosphorous containing compound is selected from the group consisting ofphosphoric acid, poly(phosphoric acid), phosphorus acid, monobutylphosphate, dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates,and combinations thereof;from 30 to 70 percent by weight of a polycarbonate; andfrom 0.01 to 20 percent by weight of an impact modifier; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another embodiment, the thermoplastic composition, comprises:

from 25 to 50 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate containing 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compound,both based on the total amount of titanium present, wherein thephosphorous containing compound is selected from the group consisting ofphosphoric acid, poly(phosphoric acid), phosphorus acid, monobutylphosphate, dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates,and combinations thereof;from 40 to 60 percent by weight of a polycarbonate;from 1 to 20 percent by weight of an impact modifier; andfrom 0.01 to 5 percent by weight of a stabilizer;wherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another embodiment, the thermoplastic composition, comprises:

from 25 to 35 percent by weight of a polybutylene terephthalate, whereinthe polybutyene terephthalate contains 50 to 300 ppm of tetraisopropyltitanate and100 to 600 ppm of phosphoric acid;from 40 to 60 percent by weight of a bisphenol A polycarbonate;from 1 to 20 percent by weight of an impact modifier comprising MBSalone or with LLDPE; andfrom 0.01 to 3 percent by weight of a stabilizer;wherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another embodiment, the invention is directed to a hydrostablethermoplastic composition, comprising:

from 25 to 35 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate contains 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compoundselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof andfrom 40 to 60 percent by weight of a polycarbonatefrom 5 to 15 percent by weight of an impact modifier or other polymer;andfrom 0.01 to 0.1 percent by weight of pentaerythritolbetalaurylthiopropionate;and 0.01 to 0.1 percent by weight of thepentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-)propionate);andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

In another embodiment, the invention is directed to a hydrostablethermoplastic composition, comprising:

from 25 to 35 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate contains 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compoundselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof; andfrom 40 to 60 percent by weight of a polycarbonatefrom 5 to 15 percent by weight of an impact modifier or other polymer;andfrom 0.01 to 3 percent by weight of an additive selected from anucleating agent, antioxidant, UV stabilizer, plasticizer, epoxycompound, melt strength additive, or a combination thereof,crosslinkers, and combinations thereof; andwherein no quencher for the catalyst complex is added to the compoundedthermoplastic composition.

A thermoplastic composition comprising the polyalkylene terephthalate asdescribed herein can be prepared by blending the components of thethermoplastic composition employing a number of procedures. In anexemplary process, the thermoplastic composition comprising apolyalkylene terephthalate prepared according to the present process, anoptional reinforcing filler, and any optional other polymers oradditives are placed into an extrusion compounder to produce moldingpellets. The components are dispersed in a matrix in the process. Inanother procedure, the components and reinforcing filler are mixed bydry blending, and then fluxed on a mill and comminuted, or extruded andchopped. The thermoplastic composition can also be mixed and directlymolded, e.g., by injection or transfer molding techniques. Specifically,all of the components are freed from as much water as possible. Inaddition, compounding is carried out to ensure that the residence timein the machine is short; the temperature is carefully controlled; thefriction heat is utilized; and an intimate blend between the componentsis obtained.

The components of the thermoplastic composition can be pre-compounded,pelletized, and then molded. Pre-compounding can be carried out inconventional equipment. For example, after pre-drying the polyestercomposition (e.g., for four hours at 120° C.), a single screw extrudercan be fed with a dry blend of the ingredients, the screw employedhaving a long transition section to ensure proper melting.Alternatively, a twin screw extruder with intermeshing co-rotatingscrews can be fed with resin and additives at the feed port andreinforcing additives (and other additives) can be fed downstream. Ineither case, a generally suitable melt temperature will be 230° C. to300° C. The pre-compounded composition can be extruded and cut up intomolding compounds such as conventional granules, pellets, and the likeby standard techniques. The composition can then be molded in anyequipment conventionally used for thermoplastic compositions capable ofinsert molding.

Thus, in another aspect, the invention is directed to a process forforming a thermoplastic composition by blending, based on the totalweight of the thermoplastic composition, the following:

from 25 to 35 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate contains 50 to 300 ppm of tetra(C₁-C₈alkyl) titanate and 100 to 600 ppm of a phosphorous containing compoundselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof; and40 to 60 percent by weight of a polycarbonatefrom 0.01 to 20 percent by weight of an impact modifier or otherpolymer; and from 0.01 to 5 percent by weight of an additive selectedfrom a nucleating agent, antioxidant, UV stabilizer, plasticizer, epoxycompound, melt strength additive, or a combination thereof,crosslinkers, and combinations thereof, wherein no quencher for thecatalyst complex is added to the compounded thermoplastic composition;andextruding, calendaring, extrusion molding, blow molding, solventcasting, or injection molding the thermoplastic composition.

Advantageously, useful articles can be made from the polyalkyleneterephthalate made according to the process described herein orthermoplastic compositions comprising the polyalkylene terephthalate. Ina specific embodiment, an article is extruded, calendared, or molded,for example blow molded or injection molded from the polyalkyleneterephthalate or composition containing the polymer. The article can bea film or a sheet. When the article is a film, the article can be formedby extrusion molding or calendaring the polyalkylene terephthalate orthermoplastic composition containing the polyester.

The thermoplastic compositions made from the present process provideproduct lines that have superior hydrolytic stability. In particular,such thermoplastic compositions can provide improved hydro and heatresistance in abusive molding and outdoor application.

As stated above, various combinations of the foregoing embodiments canbe used.

The invention is further described in the following illustrativeexamples in which all parts and percentages are by weight unlessotherwise indicated.

EXAMPLES

The following examples illustrate the scope of the invention. Theexamples and preparations which follow are provided to enable thoseskilled in the art to more clearly understand and to practice thepresent invention. They should not be considered as limiting the scopeof the invention, but merely as being illustrative and representativethereof The examples are annotated as “E.” and comparative examples areannotated hereinafter as “CE”, employed the materials listed in Table 1.

TABLE 1 Component Trade Name and Supplier BDO 1,4-Butanediol, CAS Reg.No. 110-6304, from BASF. PA Phosphoric Acid CAS Reg. No. 7664-38-2, fromAcros. TPT Tetraisopropyl titanate, CAS Reg. No. 546-68-9, from DuPont,commercial Tyzor grade DMT Dimethyl Terephthlate, CAS Reg. No.120-61-6., from Invista PE-I Polybutylene Terephthalate (PBT) sold bySABIC Innovative Plastics as VALOX  ® 315 with an intrinsic viscosity of1.2 cm³/g as measured in a 60:40 phenol/tetrachloroethane. PE-II PBTprepared by the process disclosed in Part B, below Poly- Bisphenol Apolycarbonate resin, CAS Reg. No. 25971-63- carbonate 1 5 having a Mw ofabout 30,000 g/mol, available from SABIC Innovative Plastics Plastics asPC 105 Poly- Bisphenol A polycarbonate resin available from SABICcarbonate II Innovative Plastics as LEXAN ML8199-111N AntioxidantPentaerythritol betalaurylthiopropionate, CAS Reg. No. 29598-76-3,available from Ciba Specialty Chemicals as SEENOX 412S MBSMethylmethacrylate-butadiene styrene impact modifier available asParaloid EXL-3650A from the Dow Chemical Company LLDPE Linear lowdensity polyethylene, from Nova Chemicals, Corp HinderedPentaerythritol- tetrakis(3-(3,5-di-tert-butyl-4-hydroxy- Phenolphenyl-)propionate), CAS Reg. No. 6683-19-8, available Stabilizer fromBASF Corp. Quencher Phosphorous Acid (45 percent in water), availablefrom Brenntag Mid-South, Inc.

Extrusion, Molding, and Testing

For the compositions disclosed herein, ingredients were tumble blendedand then extruded on 27 mm twin-screw extruder with a vacuum ventedmixing screw, at a barrel and die head temperature between 240 to 265°C. and a 300 rpm screw speed. The extrudate was cooled through a waterbath prior to pelletizing. ASTM tensile, Izod and flexural bars wereinjection molded on a van Dorn molding machine with a set temperature ofapproximately 240-265° C. The pellets were dried for 3-4 hours at 120°C. in a forced air-circulating oven prior to injection molding.

Notched and un-notched Izod testing was done on 75mm×12.5mm×3.2mm barsusing ASTM method D256 at both 23° C. and −30° C. using 5 lbf/ftpendulum energy.

Tensile properties were measured according to ASTM D 638 at 23° C. and50 mm/min speed for 5 mm/min for K4560 examples.

Flexural properties were tested per ASTM D790 with 3.2 mm thicknessspecimen and 1.27 min/min speed.

Specific gravity was measured per ASTM D792.

Vicat softening temperature was tested per ASTM D1525 with 10 N load and50° C./Hour temperate rate. Vicat temperature was tested on both regularmolded examples as well as abusively molded examples. Abusive moldinghere refers to molding conditions that have 15° C. higher barreltemperature and double dwelling time than regular molding.

Heat deflection temperature (HDT) was tested per ASTM D648 with 1.82 MPastress on 3.2 mm thickness specimens.

Melt volume-flow rate (MVR) was tested per ASTM D1238 at 250 ° C. with 5kg load and 240 s dwell time.

Melt viscosity was determined as a function of time at 265 ° C. for 30minutes. This test is also known as “time-sweep”. Percent viscositychange was reported.

Differential scanning calorimetry (DSC) analysis was conducted on allexamples with a ramp rate of 20° C./min and temperature range of 40 to300° C.

Hydrolysis Tests. Tensile and Izod bars were aged in a hydro-oven at 80°C. and 80% relative humidity. Specimens were drawn at 500 hours, 750hours and 1000 hours.

Part A. Reference Process for Preparing PBT

1,4-Butanediol (BDO, 10 lbs) and tetraisopropyl titanate (TPT, 9.5 mL)and additional BDO (4 lbs) was added to a Helicone reactor. Theresulting mixture was agitated under a positive pressure of nitrogen atatmospheric pressure at 130° C. for 45 minutes. Dimethyl terephthalate(DMT, 25.8 lbs) was then added to the reactor, along with additional BDO(6 lbs), and the temperature is maintained at 130° C. When the additionwas complete, the temperature was increased to 225° C. and agitation wascontinued at 67 percent of maximum.

The reaction mixture was then heated at reflux for 2 hours atapproximately 220° C. The temperature of the reaction mixture is thenincreased to 250° C. The speed of the agitator was set to 60 percent ofmaximum and the target amps of the motor was set at 3.5 amps.

The polymerization stage was then initiated. The pressure was adjustedto less than 1 torr for 180 minutes. The reaction was allowed to proceeduntil the polymer mass reached approximately 3 build. The polymer meltwas then drained out from the bottom of the reactor into a cooling bathof water at room temperature. The solidified polymer was then groundinto pellets. The resulting resin had an intrinsic viscosity of 1.25dL/min and melting temperature of 225 ° C.

Part B. Improved Process for Preparing of PBT using 1,4 Butanediol andDimethyl Terephthalate and an In-Situ Catalyst

10 pounds of 1,4-Butanediol (BDO) and 1.87 g of I M aqueous phosphoricacid were added to a Helicone reactor. The resulting mixture wasagitated under a positive pressure of nitrogen at atmospheric pressureat 130° C. After 20 minutes, 9.5 mL tetraisopropyl titanate (TPT) andadditional BDO (4 lbs) were added to the reactor. The resulting mixturewas held at 130° C. for 45 minutes. The experimental molar ratio betweenphosphoric acid and TPT was 0.65. Dimethyl terephthalate (DMT, 25.8 lbs)was then added to the reactor, along with additional BDO (6 lbs), andthe temperature was maintained at 130° C. When the addition wascomplete, the temperature was increased to 225° C. under nitrogen. Theagitator speed was then set at 67 percent of maximum.

The reaction mixture was heated at reflux for 2 hours at approximately220° C. It should be noted that the design of the overhead condensersystem did not allow a complete reflux of the BDO. As a result, in theinitial stages, about 5 to 10 lbs (2.3 to 4.5 kg) of BDO were collected.The temperature of the reaction mixture was then increased to 250° C.The speed of the agitator was set to 60 percent of maximum and thetarget amps of the motor was set at 3.5 amps.

The polymerization stage was then initiated. The pressure was adjustedto less than 1 torr for 180 minutes. The reaction was allowed to proceeduntil the polymer mass reached close to 3 build. The polymer melt wasthen drained out from the bottom of the reactor into a cooling bath ofwater at room temperature. The solidified polymer was then ground intopellets. The resulting resin had an intrinsic viscosity of 1.25 dL/minand a melting temperature of 225° C.

Part C. Hydrostability Studies of Compositions PBT Prepared According toProcess B

Because semi-crystalline polyester-polycarbonate blend products are usedin outdoor equipment housings as well as in automotive and outdoorvehicles and devices (OVAD), it is important that they are hydrostable.Hydrolysis of PBT-PC blends leads to loss of molecular weight andreduced mechanical perfomance. The presence of acid in the formulationor even the carboxyl end group of the polyesters can catalyze thedegradation of polyesters in the humid environment. Since one of thereaction products of polyester hydrolysis is itself a carboxylic acid,the hydrolytic decomposition of PBT is autocatalytic, as depictedpreviously in Scheme 1.

The transesterification reaction between polyesters and polycarbonate inthe melting state can result in the formation of copolymers, lower heatperformance, and slower crystallization. The transesterificationreaction is catalyzed by acid, base, and titanium catalyst residues inthe polyesters. Quenchers are used as additives to controltransesterification in PB-PC blends. Quenchers include “buffered” acidquenchers such as MZP [mono zinc phosphate [Zn(H₂PO₄)₂] as well asstrong acids such as phosphorous acid (H₃P0₃) and phosphoric acid(H₃PO₄). Non-acidic quenchers such as TPS [tetrapropoxysilane] have alsobeen used. EP Patent 02 72417 teaches the use of polyols as catalystquenchers. Various other polyols R—(OH), can also be used to quenchtitanium, but they lead to polymer degradation and discoloration.

We investigated whether hydrolytic stability could be improved in thePB-PC blends by using PB that is prepared using the new titanium basedcatalyst as described herein.

Table 2 summarizes the blends that were tested and their mechanicalproperties. PC-PBT blends were prepared using PBT prepared according tothe new process described herein. MBS was added as an impact modifier.Phosphorous acid (0.08 weight % of a 45% phosphorous acid in water) wasused as a quencher to prevent/control transesterification reactionbetween PC and PBT. Formulations without quenchers were also prepared.

TABLE 2 CE-1 CE-2 E-3 E-4 Item Unit Quencher No Quencher Quencher NoQuencher PC-I % 37.41 37.41 37.41 37.41 PE-I % 31.22 31.3 0 0 PC-II %19.16 19.16 19.16 19.16 Pentaeryth- % 0.05 0.05 0.05 0.05 ritol beta-laurylthio- propionate Hindered % 0.08 0.08 0.08 0.08 Phenol StabilizerPA 45% % 0.08 0 0.08 0 LLDPE % 2 2 2 2 Global MB % 10 10 10 10 PE-II % 00 31.22 31.3

As provided in Table 3, the examples showed equivalent mechanicalproperties with the respect to flexural, impact (both room temperatureand low temperature), and tensile properties. In “time-sweep” results,CE-2 showed a much higher viscosity drop (37%) after 30 minutes at 265°C. compared with other three examples. In DSC results, CE-2 clearlyshowed a much lower onset crystallization temperature (Tc) on coolingand a much smaller heat of crystallization (delta Hc) than the otherthree examples. This is a strong indication that PBT crystallizationbecomes more difficult due to chain irregularity caused by the formationof a large polyester carbonate phase due to extensivetransesterification between PBT and PC. Also, CE-2 showed a largelydecreased HDT compared to the other three examples. This can also beexplained by the lower degree of crystallinity in example CE-2.

TABLE 3 CE-1 CE-2 E-3 E-4 Item Unit Quencher No Quencher Quencher NoQuencher Flexural Modulus MPa 2090 2100 2100 2090 Flex Stress@5% StrainMPa 77 77 77 76 Flexural Stress@Yield MPa 78 78 78 78 Notched IzodDuctility, 23° C. % 100 100 100 100 Notched Izod Impact J/m 650 711 656681 Strength, 23° C. Notched Izod Ductility, −30° C. % 100 100 100 100Notched Izod Impact J/m 607 637 646 634 Strength, −30° C. Modulus ofElasticity MPa 1978 2050 1986 1954 Tensile Strength at Yield MPa 47 5151 50 Tensile Strength at Break MPa 53 54 49 55 % Elongation at Yield %4.7 4.7 4.8 4.9 % Elongation at Break % 150 150 121 152 Rheological MVRcm³/10 19 21 22 18 min Viscosity Change after time- % −17 −37 −17 −20sweep (265° C. for 30 minutes) Thermal Onset Melting Temp (Tm) ° C. 224224 224 224 Heat of Fusion/Melting (delta J/g 16.4 15.3 15.9 14 Hf)Onset Crystallization Temp ° C. 186 152 183 187 (Tc) Heat ofCrystallization (delta J/g −9.3 −3.3 −6.3 −8.5 Hc) Peak Melting Temp(Tpm) ° C. 223 218 223 223 Deflection temp ° C. 90 83 90 95 VST AfterRegular Molding ° C. 144 142 150 151 VST After Abusive Molding ° C. 14795 145 147 Delta Vicat softening % −3 47 5 4 temperature

A more ‘direct’ sign of transesterification is the delta Vicat softeningtemperature between regular molding and abusive molding. A delta Vicatlarger than 10° C. is evidence of transesterification. Comparing the 4examples tested, CE-1, E-3, and E-4 all showed a delta Vicat less than10° C. while CE-2 showed a Vicat temperature difference of 47° C. InE-4, no quencher was added. The only difference between the CE-2 and E-4compositions is how the PBT that was used in the compositions wasprepared.

The impact strength and ductility retention of the formulations weretested after hydro-aging at 80° C. and 80% relative humidity assummarized in Table 4. As provided in Table 4, E-4 substantiallymaintained its ductility after 1000 hours of hydroaging while CE-1completely lost its ductility after 750 hours aging time. Furthermore,as provided in Table 4 and FIG. 1, E-4 retained 33% of its impactstrength after 1000 hour exposure to humid environment while CE-1 almostcompletely lost its impact strength, with 4% left.

It also appears that CE-2 showed much better hydrostability comparedwith CE-1 and CE-3 and comparable hydrostability to that of E-4. Thisobservation can be explained by the formation of polyester carbonatechains and the reduction of carboxylic acid end group concentration dueto the high extent of transesteritication between two phases in CE-2.CE-2 showed inferior heat performance and much less melt stability. Thereason that E-4 showed much better hdyrostability than CE-1 is becausethe residual titanium in the PBT (PE-II) is effectively ‘deactivated’prior to blending, which eliminates the need for the acid quencheradditive. As a result, the hydrolysis resistance of PBT is improved.

TABLE 4 80° C. E-3 E-4 80% CE-1 CE-2 No No RH Properties Unit QencherQuencher Quencher Quencher t = 0 Ductility % 100 100 100 100 t =Ductility % 100 100 0 100 500 hr t = Ductility % 0 100 0 100 750 hr t =Ductility % 0 100 0 67 1000 hr t = 0 Notched J/m 607 637 646 634 ImpactStrength t = Notched J/m 269 473 56 457 500 hr Impact Strength t =Notched J/m 36 394 25 348 750 hr Impact Strength t = Notched J/m 22 28914 208 1000 hr Impact Strength

The foregoing disclosure has been described in some detail by way ofillustration and example for purposes of clarity and understanding. Theinvention has been described with reference to various specific andpreferred embodiments and techniques. However, it should be understoodthat many variations and modifications can be made while remainingwithin the spirit and scope of the invention. It will be obvious to oneof skill in the art that changes and modifications can be practicedwithin the scope of the appended claims. Therefore, it is to beunderstood that the above description is intended to be illustrative andnot restrictive. The scope of the invention should, therefore, bedetermined not with reference to the above description, but shouldinstead be determined with reference to the following appended claims,along with the full scope of equivalents to which such claims areentitled.

1. A thermoplastic composition with improved hydrostability, comprising:from 10 to 90 percent by weight of a polyalkylene terephthalate, whereinthe polyalkylene terephthalate 50 to 300 ppm of tetra(C₁-C₈ alkyl)titanate and 100 to 600 ppm of a phosphorous containing compound, bothbased on the total amount of titanium present, wherein the phosphorouscontaining compound is selected from the group consisting of phosphoricacid, poly(phosphoric acid), phosphorus acid, monobutyl phosphate,dibutyl phosphate, monoalkyl phosphates, dialkyl phosphates, andcombinations thereof; and from 10 to 90 percent by weight of apolycarbonate; and wherein the polyalkylene terephthalate is notproduced from recycled polyethylene terephthalate; wherein all weightpercents are based on the total weight of the composition; and whereinno quencher for the catalyst complex is added to the compoundedthermoplastic composition.
 2. The thermoplastic composition of claim 1,wherein the polyalkylene terephthalate is a polybutylene terephthalate.3. The thermoplastic composition of claim 1, wherein thetetra(C₁-C₈alkyl) titanate is tetraisopropyl titanate and thephosphorous containing compound is phosphoric acid.
 4. The thermoplasticcomposition of claim 1, wherein the polycarbonate is a bisphenol Apolycarbonate.
 5. The thermoplastic composition of claim 4, comprisingabout 20 to about 80 percent by weight of a bisphenol A polycarbonate.6. The thermoplastic composition of claim 1 further comprising 0.01 to 1percent by weight of a stabilizer.
 7. The thermoplastic composition ofclaim 1 further comprising 0.01 to 20 percent by weight of an impactmodifier.
 8. The thermoplastic composition of claim 7 wherein the impactmodifier comprises methylmethacrylate-butadiene-styrene copolymer aloneor with linear low density polyethylene.
 9. The thermoplasticcomposition of claim 1, further comprising a stabilizer.
 10. Thethermoplastic composition of claim 9, comprising 0.01 to 3 percent byweight of a stabilizer which is pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-)propionate) alone or incombination with pentaerythritol betalaurylthiopropionate.
 11. Thethermoplastic composition of claim 1, comprising: from 20 to 80 percentby weight of a polyalkylene terephthalate, wherein the polyalkyleneterephthalate 50 to 300 ppm of tetra(C₁-C₈ alkyl) titanate and 100 to600 ppm of a phosphorous containing compound, both based on the totalamount of titanium present, wherein the phosphorous containing compoundis selected from the group consisting of phosphoric acid,poly(phosphoric acid), phosphorus acid, monobutyl phosphate, dibutylphosphate, monoalkyl phosphates, dialkyl phosphates, and combinationsthereof; and from 20 to 80 percent by weight of a polycarbonate; and0.01 to 30 percent by weight of an impact modifier; and wherein thepolyalkylene terephthalate is not produced from recycled polyethyleneterephthalate; wherein all weight percents are based on the total weightof the composition; and wherein no quencher for the catalyst complex isadded to the compounded thermoplastic composition.
 12. The thermoplasticcomposition of claim 11, comprising: from 25 to 35 percent by weight ofa polyalkylene terephthalate, wherein the polyalkylene terephthalatecontains 50 to 300 ppm of tetra(C₁-C₈ alkyl) titanate and 100 to 600 ppmof a phosphorous containing compound, both based on the total amount oftitanium present, wherein the phosphorous containing compound isselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof; 40to 60 percent by weight of a polycarbonate; 1 to 20 percent by weight ofan impact modifier; and 0.01 to 5 percent by weight of a stabilizer;wherein the polyalkylene terephthalate is not produced from recycledpolyethylene terephthalate; wherein all weight percents are based on thetotal weight of the composition; and wherein no quencher for thecatalyst complex is added to the compounded thermoplastic composition.13. The thermoplastic composition of claim 12, comprising: from 20 to 50percent by weight of a polybutylene terephthalate, wherein thepolybutyene terephthalate contains 50 to 300 ppm of tetraisopropyltitanate and 100 to 600 ppm of phosphoric acid; 40 to 60 percent byweight of a bisphenol A polycarbonate; 1 to 20 percent by weight of animpact modifier which is a methylmethacrylate-butadiene styrene impactmodifier; and 01 to 3 percent by weight of a stabilizer; wherein thepolyalkylene terephthalate is not produced from recycled polyethyleneterephthalate; wherein all weight percents are based on the total weightof the composition; and wherein no quencher for the catalyst complex isadded to the compounded thermoplastic composition.
 14. The thermoplasticcomposition of claim 13, comprising: from 25 to 35 percent by weight ofa polyalkylene terephthalate, wherein the polyalkylene terephthalatecontains 50 to 300 ppm of tetra(C₁-C₈ alkyl) titanate and 100 to 600 ppmof a phosphorous containing compound, both based on the total amount oftitanium present, wherein the phosphorous containing compound isselected from the group consisting of phosphoric acid, poly(phosphoricacid), phosphorus acid, monobutyl phosphate, dibutyl phosphate,monoalkyl phosphates, dialkyl phosphates, and combinations thereof; andfrom 40 to 60 percent by weight of a polycarbonate from 5 to 15 percentby weight of an impact modifier or other polymer; and from 0.01 to 0.1percent by weight of pentaerythritol betalaurylthiopropionate; and from0.01 to 0.1 percent by weight ofpentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-phenyl-)propionate);and wherein the polyalkylene terephthalate is not produced from recycledpolyethylene terephthalate; wherein all weight percents are based on thetotal weight of the composition; and wherein no quencher for thecatalyst complex is added to the compounded thermoplastic composition.15. An article prepared from the thermoplastic composition of claim 1 orclaim 11.